Azo dyestuffs of the oxazine series



United States Patent ice 63,641

Patented Sept. 18, 1956 Dioxazines of the above constitution, for example, 2,763,641 those of the formula AZO DYESTUFFS OF THE OXAZINE SERIES Karl Seitz, Neu-Allschwil, and Walter Anderau, Bin- 5 (2) c1 ningen, Switzerland, assignors to Ciba Limited, Basel, N l O NH R1 NH2 Switzerland, :1 Swiss firm No Drawing. Application December 27, 1954, i V Hogs 503B Serial N0. 477,936 i H NR HN 0 Claims priority, application Switzerland m a 1 1 N December 29, 1953 6 Claims. (Cl. 260-153) t in which R1 has the meaning given above, can be made This invention prov1des new dyestutfsof the oxazine by methods in themselves known. Thus, for example,

series, which correspond to the general formula by condensing one molecular proportion of 2:3:5z6-

in which R1 represents a benzene radical, R2 represents tetrachloroquinone (chloranil) with 2 molecular propora benzene ring fused on to the hetero ring I and contions of a compound of the formula taining a sulfonic acid group, R6 represents a radical (3) H SOSH free from oxazine rings, and Y represents an amino group, a hydroxyl group or a halogen atom. HN R'NH RI NHAYI These new dyestuffs are suitable for dyeing and printin which R1 and R2 represent benzene radicals, in which ing a very wide variety of materials, for example those all the groups are in Para-Position relatively to of animal origin, such as leather, silk and wool or artione another and the Sulfonic acid group is ill Orthoiicial fibers of casein, or a superpolyamide or superpoly- Position lfilatively to the NH-R1 gr p there is urethane. They possess above all a good afiinity for 9 milled a compound of the formula cellulose-containing materials such as paper, linen, cot- (4) (31 ton, and products composed of regenerated cellulose such HOaS l as artificial silk, staple fibers and cellulose foils. Dyei;, Q ings produced on cellulose-containing materials with the new dyestuifs are in general distinguished by the purity 0 HN-Rr-HN-R1-NH-Aey1 of their tint and their good fastness to light. Moreover, so H the fastness to light is generally not impaired to any 1 a substantial extent by the usual treatments with anticreasing agents.

The invention also provides a process for making the above dyestuffs, wherein two molecular proportions of and the latter compound is treated with an agent capable of bringing about ring closure and the acyl groups are split off. The ring closure is advantageously carried out with the aid of sulfuric acid containing free sulfur cyanulnc lllahde are fi f h fi trioxide (oleum) and for splitting ofi the acyl groups it is 22331 2 ecu at proper 10H 0 a lammo' loxazme o e of advantage, for example, to treat the product at a high temperature with dilute hydrochloric acid.

As already indicated, the cyanuric halide may be reacted, for example, in the molecular ratio 2:1 with the (1) C1 diamino-dioxazine of the Formula 1, and the condensa- 0 tion product so obtained is then further condensed in the molecular ratio 1:2 with any desired monamine free 1 I I from oxazine rings. Alternatively the sequence of oper- O N ations may be reversed by condensing the halogen-compound with the monamine free from oxazine rings in equimolecular ratio, and then reacting the resulting condensation product with the diamino-dioxazine of the in which R1 represents a benzene radical, and R2 rep- Formula 1, in the molecular ratio 2:1. Any desired resents a benzene ring fused on to the hetero-ring I and primary or secondary monamine may be used, for ex containing a sulfonic acid group, and, on the other, with ample, a cyclic monamine, which contains a hetero- 2 molecular proportions of a monamine free from cyclic ring or aromatic ring, such as a naphthalene or oxazine rings, and, if desired, any halogen atoms still benzene ring, or a more highly condensed ring system, present in the triazine radical are exchanged for amino and if desired, two or more non-condensed rings which groups. may be identical or different. By suitably choosing the inonamine the tint of the final dyestutf can be influenced. Thus, for example, colorless to weakly colored monamines, or those having no dyestuff character, such as 4 reaction mixture is stirred for a further two hours at 10175! .C. The whole is allowed to cool, .the precipitated dyestufl? of the formula In this formula R3, R4 and R5 represent benzene radicals, and in the Formula 6 one X represents an azo linkage and the other X a 'CO-NH-- group. The bridge members (N=N- and CO-NH) between the benzene radicals and the amino groups are advantageously in metaor para-position relatively to one another. The benzene radicals may contain further substituents. For example, the residue R4 may contain a hydroxyl group in para-position to the'N=N- or -CONH' group and a carboxylic acid group in ortho-position to the hydroxyl group.

After the condensations with the diamino-dioxazine and the monamine have been carried out, the three halogen atoms still present in the two triazine rings may, if desired, be exchanged in known manner for hydroxyl e amine re n e e n e s t ens f the logen sempe nd it th em ne-esez n s e w th the fur. the!" am nes ma lse r ed u in k e m ner.- h fiell in ex les i ustrat nvent on t e Wi sad Peteestee s being b wei ht:

Example I Y S u o f 200 p r s of wa er .0 Pa ts 9t aceton 5, Pa Of -et ne-4'- .drex l' azebenz nex boxylic acid and 1.8 parts of anhydr us Qd llm aeeate s m e a 6- wh e stirring, w th a o ut on o Part er exenurie eh e ide i 1 Q ar s e a n ye w s s ns is orm d; a t r a ew. only fr e} amine e r n n er be e e t d, i

T a den at produc so Ob ined s then added, while stirring, to 900 parts or a blue solution of the dioxazine sulfonic acid, rendered alkaline with socli um carbonate, and which solution is prepared as deser ed e e h ho e h ed up to 4 C. and stirred at that temperature for two hours. By occasionally introducing a saturated solution of sodium car bonate dropwise care is taken that the pH value of the solution remains between 8 and 9. 25 parts of ammonia .tq f Pe e en h a e th n eer e/r 1 an is filtered off, and the latter is washed .with a S. turated solution of 'sodium'chloride. The dyestuff dyes cotton green tints of good fastness to light.

Green dyestuffs having similar properties are obtained by using, instead of 4-amino-4'-hydroxy- 1:1-azo-benzene-3-carboxylic acid, a yellow amino-monoazo-dyestulf of one of the following formulae:

CODE

H:N-C CONHC N=NQOH s5 sionzr coon $0 1 1, v sour The blue dyestufi solution mentioned above is prepared as follows:

24.6 parts of chloranil, 64.2 parts of 4-amino -4'-acetylarnino-diphenylamine-Z-sulfonic acid and 9.3 parts of magnes um oxide are stirred in 500 parts of water for vQhours at 60-65 C. There is'obtained a suspension hev nge ark blu eler- A t eeeling h u ns n; the Preei i a ed eende i n P t i filtered fi Washer! wi w ter a d dr ed in va u a .0-1Q0 C- 8-3. Part 9? he en ens t n Pr d t so obta n are ntred eed into a m xt e of 5 P r f men hyr drate and 15 parts of oleum of 27 per cent strength, and the wh le s t rre or 1 h r at room t mpe t r The, m ure is po e en to 2 P r s of i e and th diox zine sulfonic acid is filtered off with suction and Washe w t a s a e s n of m. h19: ride. The dyestuff paste is then stirred with 165 parts of hydrochloric acid of 10 per cent strength for 3 hours at 90-95 C., whereby the acetyl amino groups are hydrolysed. The resulting dyestutt solution is mixed with sodium carbonate until it becomes alkaline to Brilliant Yellow paper, and is then diluted with water to 900 parts by some Example 2 To a solution of 200 parts of water, 50 parts of acetone, 3.06 parts of 4-amino-1-hydroxybenzene-2-carboxylic acid and 1.8 parts of anhydrous sodium acetate is added at 0 Q, while stirring, a solution of 4 parts of :cyanuric chloride in 50 parts of acetone. After stirring th Whole for 15 minutes at 0 C. the primary condensatiqn Prod t i term d a e -,am r y-bengen-Z-carboxyligi acid can no longer be detected.

[Ilheaprirnary condensation product is then condensed .111 the manner described in Example 1 with the dioxagine sulfonic acid, the preparation of which is also described Example 4 in Example 1. l

The dyesmfi so Obtained corresponds to the formula 100parts ofcotton are entered at 50 C. mtoadyebath 1TH: 01 N N o BIN NH-o O-HN -OH I f 1101s 01H H, H0 NH- C-NH NH- 00H Q a Q o N c J; N H00 1 NH,

and dyes cotton pure blue tints of very good fastness which contains in 3000 parts of water 1 part of the dyeto light. stufi obtainable as described in the first and second Dyestufis having similar properties are obtained by usparagraphs of Example 1, the temperature is raised to ing, instead of 4-amino-1-hydroxybenzene-2-carboxylic 90 C. in the course of /2 hour, and 30 parts of crystalline acid, aminobenzene, cyclohexylamine, l-amino-benzene-4- sodium sulfate are added. Dyeing is then carried on for carboxylic acid, 1-amino-4-acetylaminobenzene, 4-aminoone hour at 9095 C., and there is obtained a green dye- 1:1-diphenyl, 1 amino 4 benzoylaminobenzene, 1- ing of good fastness to light. amino-4-cinnamylaminobenzene, Z-aminochrysene, 3- What is claimed is: aminopyrene or 2 (4'-aminophenyl) 6 methyl-benz- 1. A dyestufi of the oxazine series corresponding to the thiazole. formula NE, E 01 L N 0 NH-Rl-NHC 0-HNR4 a N H053 sons 1 R NHG -HN-R -NH a 1 o \N Example 3 in which R1 represents a benzene radical to which the A solution of 4 parts of cyanuric chloride in 100 parts P bPund m pm'itl'posltmn and R6 P of acetone is added at 0 C., while stirring to 900 parts of Sents an aromatlc l'adlcala weakly acetic acid solution of the dioxazine sulfonic A dyestufi of the Oxazme Semis correspondmg to the acid prepared as described in Example 1, and to which formula NH, 01 N o s HNR1NHC C--HNRo E N H038 03H 1 l R -NH HN--R NH s r o \N \C/ solution has been added a further 1.8 parts of anhydrous in which R1 represents a benzene radical to which the sodium acetate. The whole is stirred for one hour at NH- groups are bound in para-position, and Rs 0-5 C. The above solution is then poured into a solution, represents an aromatic radical of the benzene series. rendered alkaline with sodium carbonate, of 5.04 parts 3. A dyestuff of the oxazine series corresponding to the of 4 amino 4-hydroxy 1: 1'-azobenzene 3'-carboxylic formula NH: Cl ('1 N 0 *HNRrNH-C CHN-ER:-N=N R4 H 7 H0 8 sotn i, l R --N=N--R NH-O 0-HN-R -NH 4 L .lm 1 0 N o 1 NH:

acid in 500 parts of water, and the whole is heated up to in which R1 represents a benzine radical to which the 40-45" C. and stirred for 2 hours at that temperature. -NH groups are bound in para-position, R3 and R4 There are then added parts of an ammonia solution each represents abenzene radical and n represents awhole of 20 per cent strength, and the whole is stirred for a number of at the most 2. further 2 hours at -75" C. By scattering sodium 4. A dyestuff of the oxazine series corresponding to the chloride on to the mixture the dyestutf is precipitated, and formula NH: C1

L JM f 0 N I the dyestuff is filtered off after cooling and washed with 70 in which R1 represents a benzine radical to which the a saturated solution of sodium chloride. The dyestufi groups are bound in para-positron, R3 and R: d tt tint which at Similar to those of the each represents a benzene rad cal, the radical 134 contains yes co on green 5 e a hydroxyl group II]. para-position to the azo-hnkage and dyeillgs Produced y the dyestufi Obtalned as described a carboxylic acid group in ortho-position to said hydroxyl in the first and second paragraphs of Example 1. group, and n represents a whole number of at the most 2.

5. The dyestufi' of the fgrmph 11 mm?! 9? h mu References Cited in the file of this patent UNITED STATES PATENTS 2,161,622 Haller June 6, 1939 2,192,127 Ebel et al. Feb. 27, 1940 

1. A DYESTUFF OF THE OXAZINE SERIES CORRESPONDING TO THE FORMULA IN WHICH R1 REPRESENTS A BENZENE RADIFAL TO WHICH THE -NH-GROUPS ARE BOUND IN A PARA-POSITION AND R6 REPRESENTS AN AROMATIC RADICAL. 